JP2008031270A - Thermoplastic elastomer composition and molded article thereof - Google Patents

Abstract

A thermoplastic elastomer composition having excellent rubber elasticity, mechanical strength, flexibility, and heat resistance is provided.
(A) Conjugated diene polymer rubber comprising (A) conjugated diene polymer rubber, (B) ethylene / α-olefin / non-conjugated diene copolymer rubber, and (C) thermoplastic resin. The content ratio of the polymer rubber is 10 to 85 parts by mass, the content ratio of (B) ethylene / α-olefin / non-conjugated diene polymer rubber is 10 to 40 parts by mass, and (C) the content ratio of the thermoplastic resin is 5 to 5 parts. As specified in JIS-K6253, a raw material mixture of 50 parts by mass (where (A) + (B) + (C) = 100 parts by mass) is dynamically heat-treated in the presence of (D) a crosslinking agent. The thermoplastic elastomer composition has a Duro A hardness of 10 to 95 and a compression set of 40% or less after heat treatment at 70 ° C. for 22 hours as defined in JIS-K6262.
[Selection figure] None

Description

  The present invention relates to a thermoplastic elastomer composition excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance, and a molded article thereof.

  A thermoplastic elastomer composition obtained by dynamically heat-treating an ethylene / α-olefin / non-conjugated diene copolymer rubber and a thermoplastic resin in the presence of a crosslinking agent does not require a vulcanization step. For this reason, a molded article can be easily obtained by a normal thermoplastic resin molding method such as injection molding, profile extrusion molding, calendering, blow molding and the like. However, such a thermoplastic elastomer composition is also a material having the disadvantage of being inferior in elastic recovery compared to vulcanized rubber.

  In order to compensate for the above disadvantages, a thermoplastic elastomer composition using a conjugated diene polymer having a relatively sharp molecular weight distribution as a rubber component has been proposed (for example, see Patent Document 1). At this time, the conjugated diene polymer used as the rubber component is obtained by polymerization using a neodymium catalyst.

The thermoplastic elastomer composition disclosed in Patent Document 1 is excellent in rubber elasticity such as compression set and rebound resilience. However, while this thermoplastic elastomer composition is excellent in rubber elasticity, the level of heat resistance is not always sufficient. For this reason, the present condition is that the thermoplastic elastomer composition which shows rubber elasticity and heat resistance in a favorable and well-balanced manner has not yet been developed.
JP 2005-139297 A

  The present invention has been made in view of such problems of the prior art, and the subject is a thermoplastic elastomer composition excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance. And providing a molded product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors used conjugated diene polymer rubber and ethylene / α-olefin / nonconjugated diene copolymer rubber as rubber components, and in the presence of a crosslinking agent, these were used. The inventors have found that the above-mentioned problems can be achieved by dynamically heat-treating together with a thermoplastic resin, and have completed the present invention.

  That is, according to this invention, the thermoplastic elastomer composition shown below and its molded article are provided.

  [1] (A) Conjugated diene polymer rubber containing (A) conjugated diene polymer rubber, (B) ethylene / α-olefin / non-conjugated diene copolymer rubber, and (C) thermoplastic resin. The content ratio of the polymer rubber is 10 to 85 parts by mass, the content ratio of the (B) ethylene / α-olefin / non-conjugated diene polymer rubber is 10 to 40 parts by mass, and the content ratio of the (C) thermoplastic resin. 5 to 50 parts by mass (provided that (A) + (B) + (C) = 100 parts by mass) is obtained by dynamically heat-treating (D) a crosslinking agent in the presence of a crosslinking agent. A thermoplastic elastomer composition having a Duro A hardness defined by K6253 of 10 to 95 and a compression set of 40% or less after heat treatment at 70 ° C. for 22 hours defined by JIS-K6262.

  [2] The thermoplastic elastomer according to [1], wherein the (A) conjugated diene polymer rubber is obtained by polymerizing a monomer component containing a conjugated diene compound using a rare earth element compound catalyst. Composition.

[3] The thermoplastic elastomer composition according to [2], wherein the rare earth element compound-based catalyst is a catalyst mainly composed of the following components (a) to (d).
(A) Component: Rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a compound obtained by reaction of these compounds with a Lewis base (b) Component: alumoxane (c) Component: AlR ¹ R ² R ^{3 (wherein,} R 1 to R ² are the same or different and is a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{R 3} is a hydrocarbon group having 1 to 10 carbon atoms. However, ^{R 3} is , Which may be the same as or different from R ¹ or R ² ) (d) Component: a halogenated silicon compound and / or a halogenated organosilicon compound

  [4] The (A) conjugated diene polymer rubber has a 1,4-cis bond content of 90% or more and is measured by gel permeation chromatography. The weight average molecular weight (Mw) and number average molecular weight (Mn The thermoplastic elastomer composition according to any one of [1] to [3], in which a ratio (Mw / Mn) to 3.5) is 3.5 or less.

  [5] The thermoplastic resin according to any one of [1] to [4], wherein the thermoplastic resin (C) is at least one selected from the group consisting of a crystalline polyolefin resin and an amorphous polyolefin resin. Thermoplastic elastomer composition.

  [6] With respect to a total of 100 parts by mass of the (A) conjugated diene polymer rubber, the (B) ethylene / α-olefin / nonconjugated diene polymer rubber, and the (C) thermoplastic resin, // The thermoplastic elastomer composition according to any one of [1] to [5], which contains 200 parts by mass or less of a plasticizer.

  [7] A molded article comprising the thermoplastic elastomer composition according to any one of [1] to [6].

  The thermoplastic elastomer composition of the present invention has such effects as excellent rubber elasticity, mechanical strength, flexibility, and heat resistance.

  In addition, the molded product of the present invention has the effect of being excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

1. Thermoplastic elastomer composition:
One embodiment of the thermoplastic elastomer composition of the present invention comprises (A) a conjugated diene polymer rubber (hereinafter also referred to as “component (A)”) and (B) an ethylene / α-olefin / nonconjugated diene copolymer. A raw material mixture containing polymer rubber (hereinafter also referred to as “component (B)”) and (C) thermoplastic resin (hereinafter also referred to as “component (C)”) in a predetermined ratio is (D) crosslinked. Is dynamically heat-treated in the presence of an agent (hereinafter, also referred to as “component (D)”), has a durometer A hardness defined by JIS-K6253 of 10 to 95, and is defined by JIS-K6262. The compression set after heat treatment at 70 ° C. for 22 hours is 40% or less. The details will be described below.

((A) Conjugated diene polymer rubber)
The component (A) is a conjugated diene polymer rubber. As this component (A), 1,3-butadiene, 2-methyl-1,3-butadiene (hereinafter referred to as “isoprene”), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, Preferred examples include those obtained by polymerizing conjugated diene compounds such as 1,3-hexadiene and myrcene. Among these conjugated diene compounds, 1,3-butadiene and isoprene are preferable. Furthermore, as component (A), a monomer component containing these conjugated diene compounds can be suitably used which is polymerized using a rare earth element compound catalyst. Specifically, this rare earth element compound-based catalyst is a catalyst mainly comprising the following components (a) to (d).

Component (a): a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a compound obtained from the reaction of these compounds with a Lewis base (hereinafter also referred to as “(a) rare earth metal compound”)
(B) component: alumoxane (c) component: AlR ¹ R ² R ³ (wherein R ^{1 to} R ² are the same or different and are a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, and R ³ is carbon. An organoaluminum compound corresponding to the hydrocarbon group of formula 1 to 10, wherein R ³ may be the same as or different from R ¹ or R ² (d) Component: silicon halide compound And / or halogenated organosilicon compound (hereinafter also referred to as “(d) silicon compound”)

((A) rare earth compound)
The component (a) is a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table or a compound obtained from a reaction of these compounds with a Lewis base. Preferred rare earth elements are neodymium, praseodymium, cerium, lanthanum and gadolinium, more preferably neodymium. Two or more rare earth elements may be used. The rare earth element-containing compound is preferably a carboxylate, an alkoxide, a β-diketone complex, a phosphate, or a phosphite, and more preferably a carboxylate or a phosphate. Is particularly preferred.

The carboxylate of the rare earth element is, for example, a general formula (R ²³ —CO ₂ ) ₃ M (wherein M is a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ²³ has 1 to 20 hydrocarbon groups (preferably saturated or unsaturated, linear, branched, or cyclic), with the carboxyl group bonded to a primary, secondary, or tertiary carbon atom) expressed. Specifically, octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid (trade names manufactured by Shell Chemical Co., and the carboxyl group is bonded to a tertiary carbon atom. Carboxylic acid) and the like. Of these, salts of 2-ethyl-hexanoic acid, naphthenic acid, and versatic acid are preferable.

The alkoxide of the rare earth element is, for example, a general formula (R ²⁴ O) ₃ M (wherein M is a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ²⁴ is a hydrocarbon having 1 to 20 carbon atoms). Group (preferably saturated or unsaturated, linear, branched, or cyclic), and the carboxyl group is bonded to a primary, secondary, or tertiary carbon atom). Examples of the alkoxy group represented by “R ²⁴ O” include 2-ethyl-hexylalkoxy group, oleylalkoxy group, stearylalkoxy group, phenoxy group, benzylalkoxy group and the like. Of these, a 2-ethyl-hexylalkoxy group and a benzylalkoxy group are preferable.

  Examples of the rare earth element β-diketone complex include rare earth elements such as acetylacetone, benzoylacetone, propionylacetone, valerylacetone, and ethylacetylacetone complex. Of these, acetylacetone complex and ethylacetylacetone complex are preferable.

  As rare earth element phosphates or phosphites, rare earth elements bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p-nonylphenyl) phosphate, bisphosphate (Polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl, 2 -Ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2-ethylhexyl) ) Phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, etc. It can be mentioned. Of these, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and a salt of bis (2-ethylhexyl) phosphinic acid are preferable. Among those exemplified above, neodymium phosphate or neodymium carboxylate is particularly preferred, and carboxylates such as neodymium 2-ethyl-hexanoate and neodymium versatate are most preferred.

  The Lewis base used for easily solubilizing the rare earth element-containing compound in a solvent is preferably used in a ratio of 0 to 30 mol, more preferably 1 to 10 mol, per 1 mol of the rare earth element-containing compound. The Lewis base is also used as a mixture with a rare earth element-containing compound. Examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol. The above (a) component can be used individually by 1 type or in combination of 2 or more types.

((B) alumoxane)
The component (b) is a compound having a structure represented by the following formula (1) or (2). In addition, Fine Chemicals, 23, (9), 5 (1994), J. Am. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995).

In the formulas (1) and (2), R ²⁵ is a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, and n is an integer of 2 or more. Examples of R ²⁵ include methyl, ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, isohexyl, octyl, and isooctyl groups. Of these, a methyl group, an ethyl group, an isobutyl group, and a t-butyl group are preferable, and a methyl group is more preferable. N is 2 or more, preferably an integer of 4 to 100. Specific examples of the component (b) include methylalumoxane, ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane and the like. Can be mentioned.

  The component (b) may be produced using any known technique. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, water-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16-hydrate. It can manufacture by adding the salt containing crystallization water etc. and making it react. The above (b) component can be used individually by 1 type or in combination of 2 or more types.

((C) Organoaluminum compound)
Examples of the component (c) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride, ethylaluminum dihalide, n-propylaluminum dihalide, isobutyl Can be exemplified Le dihalides such. Of these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. (C) A component can be used individually by 1 type or in combination of 2 or more types.

((D) silicon compound)
The component (d) is a halogenated silicon compound and / or a halogenated organosilicon compound. Examples of the halogenated silicon compound include silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, and the like.

  Examples of the halogenated organosilicon compound include triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, triethylchlorosilane, trimethylchlorosilane, methylchlorosilane, trimethylbromosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyldisilane. Chlorosilane, dibutyldichlorosilane, diethyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, trichlorosilane, trichlorosilane Bromosilane, vinylmethyldichlorosilane, vinyldimethyl Chlorosilane, chloromethylsilane, chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, chloromethylmethyldichlorosilane, chloromethyltrichlorosilane, dichloromethylsilane, dichloromethylmethyldichlorosilane, dichloromethyldimethylchlorosilane, dichlorotetramethyldisilane, tetrachlorodimethyl Examples thereof include silane, bischlorodimethylsilylethane, dichlorotetramethyldisiloxane, trimethylsiloxydichlorosilane, trimethylsiloxydimethylchlorosilane, and tristrimethylsiloxydichlorosilane.

  As component (d), silicon tetrachloride, triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, ethyltrichlorosilane, methyltrichlorosilane, trichlorosilane, dichlorotetramethyldisilane, dichlorotetramethyldisiloxane Is preferred, and silicon tetrachloride is more preferred. The above (d) component can be used individually by 1 type or in combination of 2 or more types.

  The amount and composition ratio of each component contained in the catalyst to be used are set to various values depending on the purpose and necessity. Specifically, the component (a) is preferably used in an amount of 0.0001 to 1.0 mmol, more preferably 0.0005 to 0.5 mmol, with respect to 100 g of the conjugated diene compound. If it is less than 0.0001 mmol, the polymerization activity tends to be low. On the other hand, if it exceeds 1.0 mmol, the catalyst concentration tends to be high and a decalcification step tends to be required.

  The amount of component (b) used can be expressed as the molar ratio of Al to component (a). Component (a): Component (b) is preferably in a molar ratio of 1: 1 to 1: 500, more preferably 1: 3 to 1: 250, and 1: 5 to 1: 100. It is particularly preferable to do this. In addition, the component (a): component (c) is preferably 1: 1 to 1: 300, more preferably 1: 3 to 1: 150 in terms of a molar ratio. Component (a): Component (d) is preferably in a molar ratio of 1: 0.1 to 1:30, more preferably 1: 0.2 to 1:15.

  Outside the range of these catalyst amounts and catalyst component ratios, it may be difficult to act as a highly active catalyst, or a step of removing catalyst residues may be required. In addition to the components (a) to (d), the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.

  As the catalyst component, in addition to the components (a) to (d), a conjugated diene compound and / or a non-conjugated diene compound may be used at a ratio of 0 to 50 mol per 1 mol of the component (a) as necessary. Good. As this conjugated diene compound, 1,3-butadiene, isoprene and the like can be used as in the case of the monomer for polymerization. Examples of non-conjugated diene compounds include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene. Although it is not essential to use a conjugated diene compound or a non-conjugated diene compound as a catalyst component, the combined use has the advantage of further improving the catalyst activity.

  The catalyst can be produced, for example, by reacting the components (a) to (d) dissolved in a solvent and, if necessary, a conjugated diene compound and / or a non-conjugated diene compound. In that case, the addition order of each component may be arbitrary. Each component is preferably mixed, reacted and aged in advance from the viewpoint of improving the polymerization activity and shortening the polymerization initiation derivative period. The aging temperature is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. If it is less than 0 ° C., aging tends not to be performed sufficiently. On the other hand, if it exceeds 100 ° C., the catalyst activity tends to decrease and the molecular weight distribution tends to increase. There is no restriction | limiting in particular in age | cure | ripening time, It can also contact in a line before adding to a polymerization reaction tank. An aging time of 0.5 minutes or more is sufficient, and is stable for several days.

  Conjugated diene compounds that can be polymerized using a catalyst having components (a) to (d) as main components include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Examples include dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and myrcene. Of these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable. These conjugated diene compounds can be used singly or in combination of two or more.

  The component (A) can be produced by performing a polymerization reaction using a solvent or in the absence of a solvent. An inert organic solvent can be used as the polymerization solvent. Examples of such an organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane, and heptane; saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane; Monoolefins such as 1-butene and 2-butene; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, Mention may be made of halogenated hydrocarbons such as bromobenzene and chlorotoluene.

  The polymerization temperature is usually −30 ° C. to + 200 ° C., preferably 0 to + 150 ° C. The polymerization reaction may be batch or continuous. In addition, when using a polymerization solvent, the monomer concentration in this solvent is 5-50 mass% normally, Preferably it is 7-35 mass%. Also, in order to prevent the catalyst and polymer from being deactivated during the production of the polymer, consideration should be given so as to minimize the incorporation of a deactivating compound such as oxygen, water, or carbon dioxide in the polymerization system. Is preferred.

  When a catalyst mainly composed of components (a) to (d) is used, a conjugated diene polymer rubber (component (A)) having a high 1,4-cis bond content and a sharp molecular weight distribution can be obtained. . The 1,4-cis bond content of the component (A) obtained by using the catalyst mainly composed of the components (a) to (d) is usually 90% or more, preferably 92% or more. Further, the 1,2-vinyl bond content of the component (A) is usually 2.5% or less, preferably 2.0% or less. Outside these ranges, mechanical properties and rubber elasticity tend to decrease. The microstructure of the component (A) such as the 1,4-cis bond content can be easily adjusted by controlling the catalyst composition ratio and the polymerization temperature.

Moreover, Mw / Mn which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (A) is preferably 3.5 or less, more preferably 3.3 or less. If it exceeds 3.5, the wear resistance tends to decrease. Mw / Mn can be easily adjusted by controlling the molar ratio of the components (a) to (d). The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the component (A) is preferably 10 to 100, more preferably 15 to 90. If it is less than 10, the mechanical properties and rubber elasticity of the thermoplastic elastomer composition tend to decrease. On the other hand, if it exceeds 100, the workability during dynamic crosslinking tends to be lowered.

  The molecular weight of component (A) can be varied over a wide range. The weight average molecular weight (Mw) in terms of polystyrene of the component (A) is usually 50,000 to 1,500,000, preferably 100,000 to 1,000,000. If it is less than 50,000, the mechanical properties and rubber elasticity of the thermoplastic elastomer composition tend to decrease. On the other hand, if it exceeds 1.5 million, the workability during dynamic crosslinking tends to be lowered.

  If necessary, a polymerization terminator and a polymer stabilizer are added to the polymerization reaction system, and a drying operation is performed while using a known solvent removal in the production of a conjugated diene polymer. Conjugated diene polymer rubber can be recovered from the polymerization reaction system.

  In addition, the conjugated diene compound is polymerized using the catalyst, and subsequently, the active terminal of the obtained polymer is reacted with at least one compound selected from the group of the following components (e) to (k) (hereinafter, (Also referred to as “denaturation”). Thereby, the polymer which increased molecular weight or branched the molecular chain can be obtained. This modification improves the mechanical properties and rubber elasticity.

Component ^{_{(e): R 4 n M'X 4-n}} , M'X 4, M'X 3, R 4 n M '(- R 5 -COOR 6) 4-n, or ^R _{4 n} M' (- R ⁵ —COR ⁶ ) A halogenated organometallic compound, a halogenated metal compound, or an organometallic compound corresponding to _4-n (wherein R ⁴ and R ⁵ are the same or different, a hydrocarbon group having 1 to 20 carbon atoms, R ⁶ may contain a carbonyl group or an ester group in the side chain, the hydrocarbon group having 1 to 20 carbon atoms, M ′ is a tin atom, a silicon atom, a germanium atom, or a phosphorus atom, X is a halogen atom, n Is an integer from 0 to 3).

  (F) Component: heterocumulene compound containing a Y = C = Z bond in the molecule (where Y is a carbon atom, oxygen atom, nitrogen atom, or sulfur atom, Z is an oxygen atom, nitrogen atom, or sulfur) Atom).

  (G) Component: Hetero 3-membered ring compound containing a bond represented by the following general formula (3) in the molecule (however, in the following general formula (3), Y ′ represents an oxygen atom, a nitrogen atom, Or a sulfur atom).

  (H) Component: Halogenated isocyano compound.

(I) ^{_{component: R 7 - (COOH) m}} , R 8 (COX) m, R 9 - (COO-R 10), R 11 -OCOO-R 12, R 13 - (COOCO-R 14) m, or Carboxylic acid, acid halide, ester compound, carbonate compound, or acid anhydride corresponding to the following general formula (4) (provided that R ^{7 to} R ¹⁵ are the same or different, a hydrocarbon group having 1 to 50 carbon atoms, X is a halogen atom, and m is an integer of 1 to 5.

(J) _{^{component: R 16 l M "(OCOR}} 17) 4-l, R 18 l M" (OCOR 19 -COOR 20) 4-l, or the following general formula (5) to the metal of the corresponding carboxylic acid A salt (wherein R ^{16 to} R ²² are the same or different, a hydrocarbon group having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom, or a germanium atom, and l is an integer of 0 to 3).

  (K) Component: Compound having alkoxysilyl group

  Among the components (e), when M ′ is a tin atom, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltin Examples thereof include dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, tin tetrachloride and the like.

  Among the components (e), when M ′ is a silicon atom, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane And dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltridichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and silicon tetrachloride.

  Further, among the components (e), when M ′ is a germanium atom, for example, triphenyl germanium chloride, dibutyl germanium dichloride, diphenyl germanium dichloride, butyl germanium trichloride, germanium tetrachloride, and the like can be given. Further, among the components (e), examples of the case where M ′ is a phosphorus atom include phosphorus trichloride. In addition, you may use these (e) components together in arbitrary ratios.

  Among the components (f), a compound in which Y is a carbon atom and Z is an oxygen atom is a ketene compound, and a compound in which Y is a carbon atom and Z is a sulfur atom is a thioketene compound. A compound in which Y is a nitrogen atom and Z is an oxygen atom is an isocyanate compound, and a compound in which Y is a nitrogen atom and Z is a sulfur atom is a thioisocyanate compound. Further, a compound in which both Y and Z are nitrogen atoms is a carbodiimide compound, a compound in which both Y and Z are oxygen atoms is carbon dioxide, a compound in which Y is an oxygen atom and Z is a sulfur atom A compound that is carbonyl sulfide and both Y and Z are sulfur atoms is carbon disulfide. However, the component (f) is not limited to these examples.

  Examples of the ketene compound include ethyl ketene, butyl ketene, phenyl ketene, and toluyl ketene. Examples of the thioketene compound include ethylene thioketene, butyl thioketene, phenyl thioketene, toluyl thioketene and the like. Examples of the isocyanate compound include phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like. be able to. Examples of the thioisocyanate compound include phenylthioisocyanate, 2,4-tolylenediisocyanate, hexamethylene dithioisocyanate, and the like. Examples of the carbodiimide compound include N, N′-diphenylcarbodiimide, N, N′-ethylcarbodiimide, and the like.

  Among the components (g), the compound in which Y ′ is an oxygen atom is an epoxy compound, the compound in which Y ′ is a nitrogen atom is an ethyleneimine derivative, and the compound in which Y ′ is a sulfur atom is a thiirane compound. . Examples of the epoxy compound include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, and epoxidized natural rubber. Examples of the ethyleneimine derivative include ethyleneimine, propyleneimine, N-phenylethyleneimine, N- (β-cyanoethyl) ethyleneimine, and the like. Furthermore, examples of the thiirane compound include thiirane, methylthiirane, phenylthiirane, and the like.

  The halogenated isocyano compound as the component (h) is a compound having a structure represented by the following general formula (6) (wherein X is a halogen atom in the following general formula (6)).

  Examples of the halogenated isocyano compound include 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, and 3,6-dichloro-4. -Methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6-dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5,6-tetrachloro Pyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloropyrazine, , 4-bis (methylthio) -6-chloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2-chlorobenzothiazole , 2-chlorobenzoxazole and the like.

  Among the components (i), examples of the carboxylic acid include acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. And hydrolyzate or partial hydrolyzate of merit acid, polymethacrylic acid ester compound or polyacrylic acid compound.

  Among the components (i), acid halides include, for example, acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutanoic acid chloride, octanoic acid chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride, phthalic acid chloride, maleic acid. Examples thereof include acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, and benzoyl fluoride.

  Among the components (i), examples of the ester compound include ethyl acetate, ethyl stearate, diethyl adipate, diethyl maleate, methyl benzoate, ethyl acrylate, ethyl methacrylate, diethyl phthalate, dimethyl terephthalate, tri Examples include tributyl merit acid, tetraoctyl pyromellitic acid, hexaethyl merit acid, phenyl acetate, polymethyl methacrylate, polyethyl acrylate, polyisobutyl acrylate, and the like. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate, diphenyl carbonate, and the like.

  Among the components (i), examples of the acid anhydride include intermolecular acid anhydrides such as acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, and cinnamic acid. Intramolecular acid anhydrides such as succinic anhydride, methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, styrene-maleic anhydride copolymer represented by the general formula (5) You can list things.

  In addition, the compound illustrated as (i) component may contain aprotic polar groups, such as an ether group and a tertiary amino group, in a molecule | numerator in the range which does not impair the objective of this invention. Moreover, (i) component can also be used individually by 1 type or in mixture of 2 or more types. Further, the component (i) may contain a compound containing a free alcohol group or phenol group as an impurity.

Among the components (j), examples of the compound represented by “R ¹⁶ _l M” (OCOR ¹⁷ ) _4-l ”include triphenyl tin laurate, triphenyl tin-2-ethyl hexatate, and triphenyl tin naphthate. , Triphenyltin acetate, triphenyltin acrylate, tri-n-butyltin laurate, tri-n-butyltin-2-ethylhexarate, tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n- Butyltin acrylate, tri-t-butyltin laurate, tri-t-butyltin-2-ethylhexarate, tri-t-butyltin naphthate, tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate , Triisobutyltin-2-ethylhexa Tate, triisobutyltin naphthate, triisobutyltin acetate, triisobutyltin acrylate, triisopropyltin laurate, triisopropyltin-2-ethylhexarate, triisopropyltin naphthate, triisopropyltin acetate, triisopropyltin acrylate, Trihexyltin laurate, trihexyltin-2-ethylhexarate, trihexyltin acetate, trihexyltin acrylate, trioctyltin laurate, trioctyltin-2-ethylhexarate, trioctyltin naphthate, trioctyl Tin acetate, trioctyltin acrylate, tri-2-ethylhexyltin laurate, tri-2-ethylhexyltin-2-ethylhexarate, tri-2-eth Ruhexyltin naphthate, tri-2-ethylhexyltin acetate, tri-2-ethylhexyltin acrylate, tristearyltin laurate, tristearyltin-2-ethylhexate, tristearyltin naphthate, tristearyltin acetate, tristearyl Tin acrylate, tribenzyltin laurate, tribenzyltin-2-ethylhexarate, tribenzyltin naphthate, tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-2-ethylhexarate, diphenyltin distearate , Diphenyltin dinaphthate, diphenyltin diacetate, diphenyltin diacrylate, di-n-butyltin dilaurate, di-n-butyltin 2-ethyl hexatate, di-n-butyltin distearate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin diacrylate, di-t-butyltin dilaurate, di- t-butyltin di-2-ethylhexarate, di-t-butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di-t-butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin Di-2-ethyl hexatate, diisobutyltin distearate, diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate, diisopropyltin-2-ethylhexarate, diisopropyltin disteate Allate, diisopropyltin dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexarate, dihexyltin distearate, dihexyltin dinaphthate, dihexyltin diacetate, dihexyl Tin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-2-ethylhexarate, di-2-ethylhexyltin distearate, di-2-ethylhexyltin dinaphthate, di-2-ethylhexyl Tin diacetate, di-2-ethylhexyl tin diacrylate, dioctyl tin dilaurate, dioctyl tin di-2-ethyl hexatate, dioctyl tin distearate, dioctyl tin di Phthalate, dioctyltin diacetate, dioctyltin diacrylate, distearyltin dilaurate, distearyltin di-2-ethylhexarate, distearyltin distearate, distearyltin dinaphthate, distearyltin diacetate, distearyl Tin diacrylate, dibenzyltin dilaurate, dibenzyltin di-2-ethylhexarate, dibenzyltin distearate, dibenzyltin dinaphthate, dibenzyltin diacetate, dibenzyltin diacrylate, phenyltin trilaurate, phenyl Tin tri-2-ethyl hexatate, phenyl tin trinaphthate, phenyl tin triacetate, phenyl tin triacrylate, n-butyl tin trilaurate, n-butyl tin tri-2-e Hexhexate, n-butyltin trinaphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2-ethylhexarate, t-butyltin trinaphthate, t-butyltin triacetate, t-butyltin triacrylate, isobutyltin trilaurate, isobutyltin tri-2-ethyl hexatate, isobutyltin trinaphthate, isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri-2-ethyl Hexatate, isopropyl tin trinaphthate, isopropyl tin triacetate, isopropyl tin triacrylate, hexyl tin trilaurate, hexyl tin tri-2- Ethyl hexatate, hexyl tin trinaphthate, hexyl tin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, octyl tin trinaphthate, octyl tin triacetate, octyl tin triacrylate, 2-ethylhexyltin trilaurate, 2-ethylhexyltin tri-2-ethylhexarate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2-ethylhexyltin triacrylate, stearyltin trilaurate, stearyltin tri -2-ethyl hexatate, stearyl tin trinaphthate, stearyl tin triacetate, stearyl tin triacrylate, benzyl tin trilaurate, ben Rusuzutori 2-ethylhexanoate Tate, benzyl tin tri naphthoquinone Tate, benzyl tin triacetate, and benzyl tin triacrylate.

Further, (j) of the components, _{^{"R 18 l M" (OCO-}} R 19 -COOR 20) 4-l "Examples of the compound represented by, for example, diphenyl tin bis methyl maleate, diphenyltin bis-2-ethylhex Tate, diphenyltin bisoctyl malate, diphenyltin bisoctyl malate, diphenyltin bisbenzyl malate, di-n-butyltin bismethylmalate, di-n-butyltin bis-2-ethylhexarate, di-n-butyltin bisoctyl Malate, di-n-butyltin bisbenzyl malate, di-t-butyltin bismethylmalate, di-t-butyltin bis-2-ethylhexarate, di-t-butyltin bisoctylmalate, di-t- Butyltin bisbenzylmaleate, diisobutyltin bismethylmale , Diisobutyltin bis-2-ethylhexarate, diisobutyltin bisoctylmalate, diisobutyltin bisbenzylmalate, diisopropyltin bismethylmalate, diisopropyltin bis-2-ethylhexarate, diisopropyltin bisoctylmalate, diisopropyl Tin bisbenzylmalate, dihexyltin bismethylmalate, dihexyltin bis-2-ethylhexarate, dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di- 2-ethylhexyltin bis-2-ethylhexamate, di-2-ethylhexyltin bisoctylmalate, di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmale , Dioctyltin bis-2-ethylhexarate, dioctyltin bisoctylmalate, dioctyltin bisbenzylmalate, distearyltin bismethylmalate, distearyltin bis-2-ethylhexarate, distearyltin bis Octylmalate, distearyltin bisbenzylmalate, dibenzyltin bismethylmalate, dibenzyltin bis-2-ethylhexarate, dibenzyltin bisoctylmalate, dibenzyltin bisbenzylmalate, diphenyltin bismethyl Agitate, diphenyltin bis-2-ethylhexaate, diphenyltin bisoctyl agitate, diphenyltin bisbenzyl agitate, di-n-butyltin bismethyl agitate, di-n-butyltin bis-2-ethylhexa Tate, di-n-butyltin bisoctyl agitate, di-n-butyltin bisbenzyl agitate, di-t-butyltin bismethyl agitate, di-t-butyltin bis-2-ethylhexate, di-t-butyltin bisoctyl agitate , Di-t-butyltin bisbenzyl agitate, diisobutyltin bismethyl agitate, diisobutyltin bis-2-ethylhexaate, diisobutyltin bisoctyl agitate, diisobutyltin bisbenzyl agitate, diisopropyltin bismethyl agitate, diisopropyltin bis-2- Ethyl hexatate, diisopropyl tin bis octyl agitate, diisopropyl tin bis benzyl agitate, dihexyl tin bismethyl agitate, dihexyl tin bis-2-ethyl Xanthate, dihexyltin bismethyl agitate, dihexyltin bisbenzyl agitate, di-2-ethylhexyltin bismethyl agitate, di-2-ethylhexyltin bis-2-ethylhexate, di-2-ethylhexyltin bisoctyl agitate, di- 2-ethylhexyltin bisbenzyl agitate, dioctyltin bismethyl agitate, dioctyltin bis-2-ethylhexaate, dioctyltin bisoctyl agitate, dioctyltin bisbenzyl agitate, distearyl tin bismethyl agitate, distearyl tin bis-2- Ethyl hexatate, distearyl tin bisoctyl agitate, distearyl tin bis benzyl agitate, dibenzyl tin bismethyl agitate, dibenzyl tin bis 2-ethylhexanol Tate, dibenzyl tin bis-octyl adipate Tate, mention may be made of dibenzyl tin bis benzyl azide Tate like.

  Further, among the components (j), examples of the compound represented by the general formula (5) include diphenyltin maleate, di-n-butyltin maleate, di-t-butyltin maleate, diisobutyltin maleate, and diisopropyl. Tin malate, dihexyl tin maleate, di-2-ethylhexyl tin maleate, dioctyl tin maleate, distearyl tin maleate, dibenzyl tin maleate, diphenyltin agitate, di-n-butyltin agitate, di-t-butyltin Agitates, diisobutyltin agitates, diisopropyltin agitates, dihexyltin diacetates, di-2-ethylhexyltin agitates, dioctyltin agitates, distearyltin agitates, dibenzyltin agitates and the like.

  As the component (k), an alkoxysilane compound having at least one epoxy group and / or isocyanate group in the molecule is preferably used. Specific examples of the component (k) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, and (3-glycidyloxypropyl) methyldiethoxysilane. , Β- (3,4-epoxycyclohexyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) triethoxysilane, β- (3,4-epoxycyclohexyl) methyldimethoxysilane, β- (3,4- Epoxy group-containing alkoxysilanes such as (epoxycyclohexyl) ethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane condensate, (3-glycidyloxypropyl) methyldimethoxysilane condensate; 3-isocyanatopropyltrimethoxy Lan, 3-isocyanatopropyltriethoxysilane, (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane, condensate of 3-isocyanatopropyltrimethoxysilane, (3-isocyanate) And an isocyanate group-containing alkoxysilane compound such as a condensate of naphthopropylmethyldimethoxysilane.

  When the component (k) is reacted with the active terminal of the polymer, a Lewis acid can be added to the reaction system in order to accelerate the reaction. Lewis acid is preferable because it acts as a catalyst to accelerate the coupling reaction, improve the cold flow of the modified polymer, and improve storage stability. Specific examples of the Lewis acid include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin bis-2-ethylhexyl malate alkylmalate, dioctyltin bis-2-ethylhexyl malate, aluminum triisopropoxide and the like.

  The components (e) to (k) (hereinafter also referred to as “modifiers”) may be used alone or in combination of two or more. Here, the usage-amount of the modifier | denaturant with respect to (a) component is 0.01-200 in molar ratio, and it is still more preferable that it is 0.1-150. If it is less than 0.01, the reaction tends not to proceed sufficiently, and the effect of improving wear resistance and cold flow tends to be hardly exhibited. On the other hand, if it exceeds 200, the effect of improving physical properties is saturated, which is not economically preferable, and in some cases, toluene-insoluble matter (gel) tends to be easily generated.

  The modification reaction using the above modifier can be performed according to a method known per se. For example, the method described in JP-A-11-35633, the method described in JP-A-7-268132, and the like can be employed. After the modification reaction is completed, the target polymer is deactivated, and if necessary, a polymer stabilizer is added to the reaction system, and known solvent removal and drying operations in the production of conjugated diene polymers are performed. Can be recovered.

((B) ethylene / α-olefin / non-conjugated diene copolymer rubber)
The component (B) is an ethylene / α-olefin / non-conjugated diene copolymer rubber. The component (B) is a copolymer containing a structural unit (b1) derived from ethylene, a structural unit (b2) derived from an α-olefin, and a structural unit (b3) derived from a non-conjugated diene compound. There is no particular limitation. Furthermore, as long as the structural unit (b1), the structural unit (b2), and the structural unit (b3) are included, a multi-component copolymer including four or more different structural units may be used. In addition, (B) component can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the structural unit (b1) contained in the component (B) is preferably 35 mol% or more when the total structural unit is 100 mol%. When the proportion of the structural unit (b1) is less than 35 mol%, the mechanical strength tends to be insufficient. In addition, when there is too much ratio of a structural unit (b1), it exists in the tendency for a softness | flexibility to become inadequate. Therefore, the proportion of the structural unit (b1) contained in the component (B) is more preferably 40 to 90 mol%, particularly preferably 45 to 85 mol%, when all the structural units are 100 mol%. .

  Specific examples of the α-olefin constituting the structural unit (b2) include propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3 -Methylbutene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene and the like can be mentioned. Of these, propylene, 1-butene, and 1-octene are preferable. These α-olefins can be used alone or in combination of two or more.

  The proportion of the structural unit (b2) contained in the component (B) is preferably 5 to 65 mol%, more preferably 10 to 45 mol%, when all the structural units are 100 mol%. It is especially preferable that it is 40 mol%. When the proportion of the structural unit (a2) is less than 5 mol%, it tends to be difficult to exhibit desired rubber elasticity. On the other hand, if the proportion of the structural unit (a2) is more than 65 mol%, the durability tends to decrease.

  Specific examples of the non-conjugated diene compound constituting the structural unit (b3) include linear acyclic diene compounds such as 1,4-hexadiene, 1,5-hexadiene, and 1,6-hexadiene; 5-methyl-1 , 4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6- Branched acyclic diene compounds such as diene and dihydromyrcene; tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexene Shiriden-2-norbornene, it can be mentioned alicyclic diene compounds such as 5-vinyl-2-norbornene. Of these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferable. These non-conjugated diene compounds can be used singly or in combination of two or more.

  The proportion of the structural unit (b3) contained in the component (B) is preferably 15 mol% or less, more preferably 1 to 12 mol%, when all the structural units are 100 mol%. If the proportion of the structural unit (a3) is more than 15 mol%, the durability tends to decrease.

  As the component (B), a halogenated copolymer in which a part of the hydrogen atoms in the molecule of the component (B) described so far is substituted with a halogen atom such as a chlorine atom or a bromine atom can also be used. .

  Furthermore, as the component (B), a graft polymer obtained by polymerizing an unsaturated monomer with the component (B) described so far can also be used. As unsaturated monomers, vinyl chloride; vinyl acetate; (meth) acrylic acid; (meth) acrylic acid derivatives such as methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide; maleic acid; maleic anhydride Examples thereof include maleic acid derivatives such as acid, maleimide and dimethyl maleate; conjugated diene compounds such as butadiene, isoprene and chloroprene.

  The degree of crystallinity of the component (B) by X-ray diffraction measurement is preferably 20% or less, and more preferably 15% or less. When the crystallinity of the component (B) exceeds 20%, the flexibility tends to decrease.

  Further, as the component (B), an oil-extended rubber obtained by adding a mineral oil softener to the component (B) described so far can also be used. Such an oil-extended rubber is easy to handle. Therefore, it is preferable to use oil-extended rubber as the component (B) because the production of the thermoplastic elastomer composition becomes easy. The ratio of the ethylene / α-olefin / non-conjugated diene copolymer rubber and the mineral oil softener contained in the oil-extended rubber is 20 to 80% when the total oil-extended rubber is 100% by mass. It is preferably mass%, more preferably 25 to 75 mass%, and particularly preferably 30 to 70 mass%.

  The intrinsic viscosity (measured at 135 ° C. in decalin solvent) of the component (B) is preferably 1.0 dl / g or more. When the intrinsic viscosity of the component (B) is less than 1.0 dl / g, for example, when the aforementioned oil-extended rubber is used as the component (B), the mineral oil softener bleeds out from the thermoplastic elastomer composition. However, the rubber elasticity tends to decrease. On the other hand, when the intrinsic viscosity of the component (B) is too large, the moldability tends to be lowered. Therefore, the intrinsic viscosity of the component (B) is more preferably 2.0 to 7.0 dl / g, and particularly preferably 3.0 to 6.0 dl / g.

  The form of (A) component and (B) component is not specifically limited. That is, the form of the component (A) and the component (B) may be any of bale, crumb, pellets, and powder (including a bale pulverized product). Note that “crumb” is crumb-like or granular rubber. The crumb size is preferably 5 cm or less in terms of number average particle diameter, more preferably 4 cm or less, and particularly preferably 3 cm or less. Further, the lower limit of the number average particle diameter is usually 0.01 mm or more, preferably 0.1 mm or more, and more preferably 1 mm or more. The use of crumb having a number average particle diameter of 5 cm or less is preferable because it can be stably and quantitatively supplied to the different-direction continuous kneader when the thermoplastic elastomer composition is produced. The “powder” may be in a state obtained by solidifying and drying the rubber, or may be obtained by mechanically pulverizing crumbs or bale rubber obtained by solidifying crumbs.

((C) Thermoplastic resin)
The component (C) is a thermoplastic resin. As the component (C), aminoacrylamide polymer, crystalline polyolefin resin and its maleic anhydride graft polymer, amorphous polyolefin resin and its maleic anhydride graft polymer, polyisobutylene, ethylene vinyl chloride polymer, ethylene Vinyl alcohol polymer and its ionomer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid copolymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4-methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, acrylic resin, methacrylic resin , Vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, vinyl acetal resin, methyl methacrylate resin, fluorine resin, polyether resin, polyethylene terephthalate, polyacrylate ester, polyamide resin, hydrogenated diene polymer, etc. Can do. Among these, (c1) crystalline polyolefin resin and (c2) amorphous polyolefin resin are preferable.

((C1) crystalline polyolefin resin)
(C1) The crystalline polyolefin resin (hereinafter, also referred to as “component (c1)”) is not particularly limited, but those having an α-olefin as a main component are preferably used. That is, when the total monomer component constituting the component (c1) is 100 mol%, the α-olefin ratio is preferably 80 mol% or more, and more preferably 90 mol% or more. The component (c1) may be a homopolymer of α-olefin or a copolymer of two or more α-olefins, and may be a copolymer of α-olefin and a monomer other than α-olefin. It may be a coalescence. Moreover, the mixture of these 2 or more types of different polymers and / or copolymers may be sufficient.

  As the α-olefin constituting the component (c1), it is preferable to use an α-olefin having 2 or more carbon atoms, and it is more preferable to use an α-olefin having 2 to 12 carbon atoms.

  As the α-olefin, ethylene, propene (hereinafter referred to as “propylene”), 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl- C2-C12 alpha olefins, such as 1-pentene, 3-ethyl- 1-pentene, 1-octene, 1-decene, 1-undecene, can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, organic peroxide decay type propylene and / or 1-butene is preferably used.

  When the component (c1) is a copolymer, the copolymer may be a random copolymer or a block copolymer. However, in order to obtain an appropriate crystallinity, in the case of a random copolymer, when the content ratio of the structural unit excluding the structural unit derived from the α-olefin is 100 mol% of the entire random copolymer, 15 mol% or less, preferably 10 mol% or less. On the other hand, in the case of a block copolymer, the content of the structural unit excluding the structural unit derived from α-olefin is preferably 40 mol% or less when the entire block copolymer is 100 mol%, More preferably, it is 20 mol% or less.

  The random copolymer as described above requires, for example, a monomer component containing an α-olefin in the presence of a catalyst system containing a Ziegler-Natta catalyst, a soluble vanadium compound, an organoaluminum compound, and a solvent. Accordingly, it can be obtained by a polymerization method using a medium / low pressure method such as a method of polymerizing while supplying hydrogen as a molecular weight regulator. This polymerization can also be performed by a gas phase method (fluidized bed or stirred bed) or a liquid phase method (slurry method or solution method).

As the soluble vanadium compound, for example, a reaction product of VOCl ₃ and / or VCl ₄ and an alcohol is preferably used. As alcohol, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol, etc. should be used. Can do. Especially, a C3-C8 alcohol can be used suitably.

  Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, butyl. Examples thereof include aluminum dichloride, methylaluminoxane which is a reaction product of trimethylaluminum and water. Of these, ethylaluminum sesquichloride, butylaluminum sesquichloride, a mixture of ethylaluminum sesquichloride and triisobutylaluminum, and a mixture of triisobutylaluminum and butylaluminum sesquichloride can be suitably used.

  Furthermore, a hydrocarbon can be used as the solvent. Among these, n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane can be suitably used. These can be used individually by 1 type or in combination of 2 or more types.

  On the other hand, the block copolymer as described above can be obtained, for example, by a living polymerization method using a Ziegler-Natta catalyst.

The component (c1) has crystallinity. The crystallinity of the component (c1) measured by X-ray diffraction is preferably 50% or more, more preferably 53% or more, and particularly preferably 55% or more. The crystallinity is closely related to the density. For example, in the case of polypropylene, the density of α-type crystal (monoclinic crystal) is 0.936 g / cm ³ , the density of smectic crystal (crystal quasi-hexagonal) is 0.886 g / cm ³ , and an amorphous (atactic) component The density of is 0.850 g / cm ³ . Furthermore, in the case of poly-1-butene, the density of the isotactic crystal component is 0.91 g / cm ^3, the density of the amorphous (atactic) component is 0.87 g / cm ^3. Therefore, the degree of crystallinity to be obtained more than 50% of component (c1) is preferably in a density 0.89 g / cm ³ or more, to 0.90~0.94g / cm ³ Is more preferable. When the crystallinity is less than 50% or the density is less than 0.89 g / cm ³ , the heat resistance, strength and the like tend to be lowered.

The maximum peak temperature of the component (c1) measured by the differential scanning calorimetry, that is, the melting point (hereinafter referred to as “T _m ”) is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher. . When _Tm is less than 100 ° C., sufficient heat resistance and strength tend not to be exhibited.

  The melt flow rate (hereinafter referred to as “MFR”) of the component (c) at a temperature of 230 ° C. and a load of 2.16 kg is preferably 0.1 to 1000 g / 10 minutes, More preferably, it is -500g / 10min, and it is especially preferable that it is 1-100g / 10min. If the MFR is less than 0.1 g / 10 min, the kneadability and extrusion processability of the thermoplastic elastomer composition tend to be insufficient. On the other hand, if it exceeds 1000 g / 10 minutes, the strength tends to decrease.

Therefore, as the component (c1), the crystallinity is 50% or more, the density is 0.89 g / cm ³ or more, the ethylene unit content is 20 mol% or less, the _Tm is 100 ° C. or more, and the MFR is 0.1 It is particularly preferred to use polypropylene and / or a copolymer of propylene and ethylene that is ˜100 g / 10 min.

((C2) Amorphous polyolefin resin)
The (c2) amorphous polyolefin resin (hereinafter also referred to as “component (c2)”) is not particularly limited, but an α-olefin-based component is preferably used. That is, when the total monomer component constituting the component (c2) is 100 mol%, the proportion of α-olefin is preferably 50 mol% or more, and more preferably 60 mol% or more. The component (c2) may be a homopolymer of α-olefin or a copolymer of two or more α-olefins, and may be a copolymer of α-olefin and a monomer other than α-olefin. It may be a coalescence. Moreover, the mixture of these 2 or more types of different polymers and / or copolymers may be sufficient.

  As the α-olefin constituting the component (c2), an α-olefin having 3 or more carbon atoms is preferably used, and the same carbon number 3 as exemplified as the α-olefin constituting the component (c1) described above. More preferably, ˜12 α-olefins are used.

  Specific examples of the component (c2) include homopolymers such as atactic polypropylene and atactic poly-1-butene; propylene (containing 50 mol% or more) and other α-olefins (ethylene, 1-butene, 1-pentene). , 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.); 1-butene (containing 50 mol% or more) and other α-olefins (ethylene, propylene, 1- Pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like) and the like.

  When the component (c2) is a copolymer, this copolymer may be a random copolymer or a block copolymer. However, in the case of a block copolymer, an α-olefin unit (for example, a propylene unit or 1-butene unit) as a main component needs to be bonded with an atactic structure. In addition, when the component (c2) is a copolymer of an α-olefin having 3 or more carbon atoms and ethylene, when the total monomer component constituting the entire copolymer is 100 mol%, the α-olefin The ratio is preferably 50 mol% or more, more preferably 60 to 100 mol%.

  This atactic polypropylene can be obtained as a byproduct of polypropylene that can be used as the component (c1). Atactic polypropylene and atactic poly-1-butene can also be obtained by a polymerization method using a zirconocene compound-methylaluminoxane catalyst. On the other hand, a random copolymer can be obtained by the same method as the component (c1). The block copolymer can be obtained by a living polymerization method using a Ziegler-Natta catalyst.

The crystallinity of the component (c2) measured by X-ray diffraction is preferably less than 50%, more preferably 30% or less, and particularly preferably 20% or less. This crystallinity is closely related to the density. For this reason, it is preferable that the density of (c2) component is 0.85-0.89 g / cm < ³ >, and it is still more preferable that it is 0.85-0.88 g / cm < ³ >. The number average molecular weight M _n of the component (c2) is preferably 1000 to 20000, and more preferably 1500 to 15000. As the component (C), only one of the component (c1) and the component (c2) may be used, or two or more of these may be used in combination.

(Ratio of (A) component, (B) component, and (C) component)
The ratio of the component (A) (contained in the raw material mixture) in the thermoplastic elastomer composition of the present embodiment is 10 to 85 masses when the total of the components (A) to (C) is 100 parts by mass. Part, preferably 15 to 80 parts by mass, more preferably 20 to 75 parts by mass. When the proportion of the component (A) is less than 10 parts by mass, the elasticity of the resulting thermoplastic elastomer composition tends to decrease. On the other hand, when the ratio of the component (A) is more than 85 parts by mass, the heat resistance of the finally obtained thermoplastic elastomer composition tends to decrease.

  In addition, the ratio of the component (B) (contained in the raw material mixture) in the thermoplastic elastomer composition of the present embodiment is 10 to 10 parts when the total of the components (A) to (C) is 100 parts by mass. 40 parts by mass, preferably 12 to 38 parts by mass, and more preferably 15 to 35 parts by mass. When the proportion of the component (B) is less than 10 parts by mass, the heat resistance of the resulting thermoplastic elastomer composition tends to decrease. On the other hand, when the proportion of the component (B) is more than 40 parts by mass, the rubber elasticity of the finally obtained thermoplastic elastomer composition tends to decrease.

  The ratio of the component (C) (contained in the raw material mixture) in the thermoplastic elastomer composition of the present embodiment is 5 to 50 masses when the total of the components (A) to (C) is 100 parts by mass. Part, preferably 8 to 45 parts by mass, more preferably 10 to 40 parts. When the proportion of the component (C) is less than 5 parts by mass, the phase structure (morphology) of the thermoplastic elastomer composition finally obtained is a good sea-island structure (( C) The component is not the sea (matrix) and the cross-linked elastomer component is the island (domain)), and the molding processability and the mechanical properties may be lowered. On the other hand, when the proportion of the component (C) is more than 50 parts by mass, the flexibility and rubber elasticity of the resulting thermoplastic elastomer composition tend to decrease.

((D) Crosslinking agent)
In the thermoplastic elastomer composition of the present embodiment, the raw material mixture containing the component (A), the component (B), and the component (C) is dynamically heat-treated in the presence of the component (D) that is a crosslinking agent. It will be. Here, “dynamically heat-treating” refers to both applying a shearing force and heating. The thermoplastic elastomer composition of the present embodiment obtained by such dynamic heat treatment specifically has the component (C) as the sea phase, and the particles of the component (A) A so-called sea-island structure is formed in which the particles of the component (B) are dispersed as island phases. The type of the crosslinking agent (component (D)) is not particularly limited. For example, organic peroxides, phenol resins, sulfur, sulfur compounds, p-quinones, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, Examples include silane compounds, amino resins, polyol crosslinking agents, polyamines, triazine compounds, and metal soaps. Especially, an organic peroxide and a phenol resin can be used suitably. In addition, these crosslinking agents can also be used together.

  Examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy)- p-isopropylbenzene, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide, p-menthane peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl Okishido, benzoyl peroxide, may be mentioned di (t-butylperoxy) perbenzoate, n- butyl-4,4-bis (t-butylperoxy) valerate, and t-butyl peroxy isopropyl carbonate. Among them, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- Those having a relatively high decomposition temperature, such as di (t-butylperoxy) hexane, can be suitably used. These organic peroxides can be used alone or in combination of two or more.

  Examples of the phenol resin include a p-substituted phenol compound represented by the following general formula (7), an o-substituted phenol / aldehyde condensate, an m-substituted phenol / aldehyde condensate, a brominated alkylphenol / aldehyde condensate, and the like. Can be mentioned. Of these, p-substituted phenolic compounds are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  In said general formula (7), X is a hydroxyl group, a halogenated alkyl group, or a halogen atom, R is a C1-C15 saturated hydrocarbon group, and n is an integer of 0-10. The p-substituted phenol compound can be obtained by a condensation reaction between a p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst.

  (D) When using an organic peroxide as a component, the usage-amount of this organic peroxide is 0.05-10 mass parts with respect to a total of 100 mass parts of (A)-(C) component. It is preferable to make it 0.1 to 5 parts by mass. When the amount of the organic peroxide used is less than 0.05 parts by mass, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition tend to be reduced. On the other hand, when the amount of the organic peroxide used exceeds 10 parts by mass, the degree of crosslinking becomes excessively high, the molding processability is lowered, and the mechanical properties of the resulting thermoplastic elastomer composition tend to be lowered. .

  Moreover, when using a phenol resin as (D) component, the usage-amount of this phenol resin shall be 0.2-10 mass parts with respect to a total of 100 mass parts of (A)-(C) component. Is preferable, and it is still more preferable to set it as 0.5-5 mass parts. When the amount of the phenol resin used is less than 0.2, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition tend to be lowered. On the other hand, when the amount of the phenol resin used exceeds 10 parts by mass, the moldability tends to be lowered.

  It is preferable to use a crosslinking aid and / or a crosslinking accelerator together with the crosslinking agent because the crosslinking reaction can be performed gently and uniform crosslinking can be formed. When organic peroxide is used as a crosslinking agent, sulfur, sulfur compounds (powder sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, etc.), oxime compounds are used as crosslinking aids. (P-quinone oxime, p, p′-dibenzoylquinone oxime, etc.), polyfunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene) Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N′-m-phenylenebismaleimide, N N'- toluylene bismaleimide, maleic anhydride, divinylbenzene, the use of di (meth) zinc acrylate and the like) or the like. Of these, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide, and divinylbenzene are preferable. These can be used individually by 1 type or in combination of 2 or more types. Note that N, N′-m-phenylenebismaleimide exhibits an action as a crosslinking agent, and therefore can be used alone as a crosslinking agent.

  When using an organic peroxide as a crosslinking agent, the amount of crosslinking aid used may be 10 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C) contained in the mixture. Preferably, it is more preferable to set it as 0.2-5 mass parts. When the amount of the crosslinking aid used is more than 10 parts by mass, the degree of crosslinking becomes excessively high, the molding processability is lowered, and the mechanical properties of the resulting thermoplastic elastomer composition tend to be lowered.

  When phenol resin is used as a crosslinking agent, metal halides (such as stannous chloride and ferric chloride), organic halides (such as chlorinated polypropylene, butyl bromide rubber, and chloroprene rubber) are used as crosslinking accelerators. When used, it is preferable because the crosslinking rate can be adjusted. In addition to the crosslinking accelerator, it is more desirable to use a metal oxide such as zinc oxide or a dispersant such as stearic acid.

(Softener, plasticizer)
The thermoplastic elastomer composition of the present embodiment can contain a softener and a plasticizer as needed within a range not impairing the effects of the present invention. Examples of softeners include petroleum oils such as aromatic oil, naphthenic oil, paraffin oil, white oil, petrolatum, gilsonite, black sub, white sub, castor oil, cottonseed oil, rapeseed oil, palm oil, coconut oil, rosin And vegetable oil-based softeners such as

  Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; Adipate, diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di -Fatty acid esters such as (2-ethylhexyl) sebacate and diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid Trimellitic acid esters such as tilester, trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, tristearyl phosphate, tri -(2-ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, polyether ester and the like can be mentioned. In addition, these softeners and plasticizers described above can be used alone or in combination of two or more.

  The total use ratio of the softener and the plasticizer is usually 100 parts by mass or less, preferably 95 parts by mass or less, more preferably 90 parts by mass or less, with respect to 100 parts by mass in total of the components (A) to (C). It is. When it exceeds 100 parts by mass, the softening agent and / or plasticizer tends to bleed out from the finally obtained thermoplastic elastomer composition, and mechanical strength and rubber elasticity tend to decrease.

(Other additives)
In addition, the thermoplastic elastomer composition of the present embodiment includes a polymer compound such as rubber or thermoplastic elastomer other than the components (A) to (C) as long as it does not impair the effects of the present invention. It can be included. The polymer compound that can be contained is not particularly limited as long as it is other than the specific functional group-containing copolymer. Specifically, styrene / butadiene rubber, isoprene rubber, styrene / isoprene rubber, nitrile rubber and hydrogenated products thereof, acrylic rubber, silicone rubber, fluorine rubber, butyl rubber, natural rubber, chloroprene rubber, norbornene rubber, chlorosulfonated polyethylene , Urethane rubber, polysulfide rubber epichlorohydrin rubber, simple blend type olefin thermoplastic elastomer, implant type olefin thermoplastic elastomer, dynamically cross-linked olefin thermoplastic elastomer, polyvinyl chloride thermoplastic elastomer, styrene / butadiene Block copolymer, hydrogenated styrene / butadiene block copolymer, styrene / isoprene block copolymer, hydrogenated styrene / isoprene block copolymer, hydrogenated butadiene block copolymer, polyureta Can be mentioned system thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, fluorine-based thermoplastic elastomers, syndiotactic 1,2-polybutadiene.

  These high molecular compounds can be used individually by 1 type or in combination of 2 or more types. In addition, it is preferable that the usage-amount of a high molecular compound shall be 0-30 mass parts with respect to a total of 100 mass parts of (A)-(C) component.

  Furthermore, the thermoplastic elastomer composition of the present embodiment can contain various additives as long as the effects of the present invention are not impaired. Examples of additives that can be included include lubricants, anti-aging agents, heat stabilizers, weathering agents, metal deactivators, UV absorbers, light stabilizers, copper damage inhibitors, antibacterial / Fungicides, dispersants, crystal nucleating agents, flame retardants, tackifiers, foaming aids, colorants such as titanium oxide, carbon black, pigments, metal powders such as ferrite, inorganic fibers such as glass fibers and metal fibers, Carbon fibers, organic fibers such as aramid fibers, composite fibers, inorganic whiskers such as potassium titanate whiskers, glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, silica, alumina, alumina silica, calcium silicate , Hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton flock, cork powder, barium sulfate, fluororesin, Fillers such Rimabizu, or mixtures thereof, polyolefin waxes, cellulose powder, rubber powder, fillers and wood meal can include low molecular weight polymers.

(Preparation of thermoplastic elastomer composition)
For example, the thermoplastic elastomer composition of the present embodiment is obtained by adding the component (D) to the raw material mixture containing the components (A) to (C) and supplying the mixture to a continuous extruder or a closed kneader. It can be manufactured by heat treatment.

  As a device used for “dynamic heat treatment”, a melt kneader or the like can be cited as a suitable example. The treatment by the melt kneader may be either a continuous type or a batch type. Specific examples of the melt kneader include an open type mixing roll, a non-open type Banbury mixer, a single screw extruder, a twin screw extruder, a continuous kneader, and a pressure kneader. Among these, it is preferable to use a continuous melt kneader such as a single screw extruder, a twin screw extruder, or a continuous kneader from the viewpoints of economy, processing efficiency, and the like. Further, two or more continuous melt-kneading apparatuses of the same type or different types may be used in combination.

  The L / D ratio (ratio between the screw effective length L and the outer diameter D) of the twin screw extruder is preferably 30 or more, and more preferably 36 to 60. In addition, as the twin screw extruder, for example, an arbitrary twin screw extruder such as one in which two screws mesh or not mesh can be used, but the rotation direction of the two screws is the same direction. Are more preferable. As such a twin screw extruder, for example, a trade name “PCM” (manufactured by Ikegai Co., Ltd.), a trade name “KTX” (manufactured by Kobe Steel), a trade name “TEX” (manufactured by Nippon Steel Works), a product The name “TEM” (manufactured by Toshiba Machine Co., Ltd.), the product name “ZSK” (manufactured by Warner), and the like can be mentioned.

  The L / D ratio (ratio between the screw effective length L and the outer diameter D) of the continuous kneader is preferably 5 or more, and more preferably 10 or more. Examples of such a continuous kneader include a trade name “Mixtron KTX / LCM / NCM” (manufactured by Kobe Steel), a trade name “CIM / CMP” (manufactured by Nippon Steel).

  The treatment temperature for the dynamic heat treatment is preferably 120 to 350 ° C, and more preferably 150 to 290 ° C. The treatment time is preferably 20 seconds to 320 minutes, more preferably 30 seconds to 25 minutes. Further, the shearing force to be applied is preferably 10 to 20000 / sec, more preferably 100 to 10,000 / sec in terms of shear rate.

  The thermoplastic elastomer composition of this embodiment produced as described above has a duro A hardness defined by JIS-K6253 of 10 to 95, preferably 15 to 90, and more preferably 20 to 85. . The thermoplastic elastomer composition of the present embodiment has a compression set of 40% or less, preferably 38% or less, more preferably 35, after heat treatment at 70 ° C. for 22 hours as defined in JIS-K6262. % Or less. Therefore, if the thermoplastic elastomer composition of this embodiment is used, a molded article excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance can be produced.

2. Molding:
Next, an embodiment of the molded product of the present invention will be described. The molded article of this embodiment is obtained by molding any of the above-mentioned thermoplastic elastomer compositions. Therefore, the molded product of this embodiment is excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance.

  The process for producing the molded product of the present embodiment comprises the steps (A) to (C), (D), and other ingredients used as necessary by mixing the raw materials with the raw materials. A first step of preparing the thermoplastic elastomer composition, and a second step of molding the prepared thermoplastic elastomer composition. However, these two steps can be carried out independently, but may be carried out as a single step.

  The method for molding the thermoplastic elastomer composition as a raw material is not particularly limited, but an extrusion molding method, a calendar molding method, a solvent casting method, an injection molding method, a vacuum molding method, a powder slush molding method, a heating press method, etc. are suitable. As an example.

  The molded article of this embodiment may be a laminated molded article laminated and bonded to rubber, plastic, thermoplastic elastomer, glass, metal, cloth, wood, or the like.

  Examples of the rubber include ethylene / α-olefin / non-conjugated diene copolymer rubber and its maleic anhydride graft polymer, ethylene / α-olefin / non-conjugated diene copolymer rubber, styrene / butadiene rubber, Ni catalyst-polymerized butadiene rubber, Examples include isoprene rubber, nitrile rubber and hydrogenated products thereof, acrylic rubber, silicone rubber, fluorine rubber, butyl rubber, and natural rubber.

  Examples of the plastic include ionomer, aminoacrylamide polymer, polyethylene and its maleic anhydride graft polymer, polyisobutylene, ethylene vinyl chloride polymer, ethylene vinyl alcohol polymer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid. Copolymer, polypropylene and its maleic anhydride graft polymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4-methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin ASA resin, MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl chloride Redene resin, vinyl alcohol resin, vinyl acetal resin, methyl methacrylate resin, fluorine resin, polyether resin, polyethylene terephthalate, polyacrylate ester, polyamide resin, polyurethane, polyimide, polyurea resin, epoxy resin, phenol resin, urea resin , Polybutene-1, methylpentene resin, polyacrylonitrile and the like.

  Thermoplastic elastomers include chlorinated polyethylene thermoplastic elastomer, syndiotactic-1,2 polybutadiene, simple blend olefin thermoplastic elastomer, implant olefin thermoplastic elastomer, dynamically cross-linked olefin thermoplastic elastomer, Polyvinyl chloride thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, fluorine thermoplastic elastomer, hydrogenated styrene / butadiene rubber, hydrogenated styrene / butadiene rubber Maleic anhydride graft polymer, Hydrogenated butadiene rubber, Maleic anhydride graft polymer of Hydrogenated butadiene rubber, Hydrogenated isoprene rubber, Maleic anhydride of hydrogenated isoprene rubber Raft polymer, hydrogenated styrene / isoprene rubber, maleic anhydride graft polymer of hydrogenated styrene / isoprene rubber, hydrogenated styrene / butadiene block copolymer, water of styrene / isoprene block copolymer Additives and the like can be mentioned.

  Examples of the metal include stainless steel, aluminum, iron, copper, nickel, zinc, lead, tin, and the like, as well as nickel-zinc alloys, iron-zinc alloys, lead used in automobiles, ships, home appliances, etc. -Alloys, such as a tin alloy, can be mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

  [Hardness (Duro A)]: Measured according to JIS-K6253 and used as an index of flexibility.

  [Tensile stress, tensile breaking strength, tensile breaking elongation]: Measured according to JIS K6251.

  [Melt flow rate (MFR)]: Measured under conditions of 230 ° C. and 98 N load in accordance with JIS-K7210, and used as an index of fluidity.

  [Compression set]: Based on JIS-K6262, the value after heat treatment at 70 ° C. for 22 hours was measured and used as an index of rubber elasticity.

[Mooney viscosity (ML _{1 + 4} , 100 ° C.)]: Measured according to JIS-K6300 using an L rotor under conditions of preheating for 1 minute, rotor operating time of 4 minutes, and temperature of 100 ° C.

[Number average molecular weight (Mn), weight average molecular weight (Mw)]: Using gel permeation chromatograph (trade name “HLC-8120GPC” (manufactured by Tosoh Corporation)), differential refraction as a detector under the following conditions Measured using a meter.
Column: Trade name “GMHHXL” (manufactured by Tosoh Corporation)
Mobile phase: Tetrahydrofuran

  [1,4-cis bond content, 1,2-cis bond content]: Calculated by the Morero method using infrared analysis.

  [Heat aging test]: After carrying out a heat aging test that was allowed to stand at 80 ° C. for 1000 hours in accordance with JIS-K6257, tensile rupture strength and tensile rupture elongation were measured. The ratio of the value after the heat aging test to the value before the heat aging test was calculated as the tensile rupture strength change rate (%) and the tensile rupture elongation change rate, respectively.

(Production of butadiene rubber-1)
After dropping 0.2 mmol of 2-ethylhexanol into a 100 ml three-necked flask containing 0.1 mmol of zinc chloride, the mixture was heated to 100 ° C. and reacted for 2 hours. After completion of the reaction, 50 ml of toluene was added to prepare a toluene solution of zinc chloride in 2-ethylhexanol complex. A nitrogen-substituted autoclave with an internal volume of 5 liters was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under nitrogen. Next, 0.04 mmol of neodymium versatate in cyclohexane, 2.4 mmol of methylalumoxane, 4.0 mmol of diisobutylaluminum hydride, and 0.04 mmol of toluene solution of 2-ethylhexanol complex of zinc chloride were added to 5 of neodymium. A double amount of 1,3-butadiene and a catalyst aged at 50 ° C. for 30 minutes were charged, and polymerization was carried out at 50 ° C. for 60 minutes. The polymerization conversion of 1,3-butadiene was almost 100%. In order to measure Mooney viscosity, a part of the polymerization solution was extracted, solidified and dried. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) was 25, the 1,4-cis bond content was 97.0%, the 1,2-vinyl bond content was 1.2%, and the Mw / Mn was 2.5.

Next, while maintaining the temperature of the polymerization solution at 50 ° C., 7.2 mmol of dioctyltin bis-2-ethylhexyl malate was added, and then allowed to stand for 30 minutes. A methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added to terminate the polymerization, and then the solvent was removed by steam stripping, followed by drying with a roll at 110 ° C. Got rubber. The resulting butadiene rubber had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 39, a 1,4-cis bond content of 97.0%, a 1,2-vinyl bond content of 1.2%, and an Mw / Mn of 2. It was 8.

(Production of butadiene rubber-2)
An autoclave with an internal volume of 5 liters purged with nitrogen was charged with 2.5 kg of cyclohexane and 300 g of 1,3-butadiene under nitrogen. Next, 0.11 mmol of neodymium neodecanoate in cyclohexane, 1.5 mmol of methylalumoxane in toluene, 3.3 mmol of diisobutylaluminum hydride in cyclohexane, and 0.22 mmol of methyldichlorosilane in cyclohexane were mixed together. 30 times mole of 1,3-butadiene (5.40 mmol) and a catalyst which was aged by reaction at 25 ° C. for 30 minutes were charged and polymerized at 50 ° C. for 30 minutes. The polymerization conversion of 1,3-butadiene was almost 100%. Next, the temperature of the polymerization solution was kept at 50 ° C., 1.10 mmol of 3-glycidyloxypropyltrimethoxysilane and 0.20 mmol of dioctyltin bis-2-ethylhexyl malate were added, and then left for 30 minutes. A methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added to stop the polymerization, and then the solvent was removed by steam stripping, followed by drying with a roll at 110 ° C. Got rubber. The resulting butadiene rubber had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 55, a 1,4-cis bond content of 96.5%, a 1,2-vinyl bond content of 1.0%, and an Mw / Mn of 3. 0.

(Oil-extended rubber (ethylene / propylene / 5-ethylidene-2-norbornene terpolymer))
An ethylene / propylene / 5-ethylidene-2-norbornene terpolymer having an ethylene unit amount of 66 mol% and a 5-ethylidene-2-norbornene unit amount of 4.5 mol% was prepared. The intrinsic viscosity (measured in decalin solvent at 135 ° C.) of the obtained ethylene / propylene / 5-ethylidene-2-norbornene terpolymer was 4.7 dl / g. An oil-extended rubber was prepared by adding a mineral oil-based softener (trade name “Diana Process Oil PW-380”, manufactured by Idemitsu Kosan Co., Ltd.) to the cyclohexane solution of the ternary copolymer and then removing the solvent. . In addition, content of a mineral oil type softening agent with respect to 100 parts of ternary copolymers is 100 parts. The property of the terpolymer is crumb.

(Example 1)
46 parts of butadiene rubber, 54 parts of oil-extended rubber, 27 parts of polypropylene (crystalline polyolefin resin, trade name “NOVATEC PP BC06C”, manufactured by Nippon Polychem), anti-aging agent (trade name “Irganox 1010”, Ciba Specialty A 10-liter double-armed pressure kneader (Molyama) heated to 150 ° C. with 0.1 part of Chemicals) and 14 parts of a mineral oil softener (trade name “Diana Process Oil PW90”, manufactured by Idemitsu Kosan Co., Ltd.) And melted at 40 rpm (shear rate 200 / sec) for 20 minutes to obtain a composition in a molten state. The obtained composition was pelletized using a feeder ruder (manufactured by Moriyama Co., Ltd.) set at 180 ° C. and 40 rpm.

In the pelletized composition, 1 part of a crosslinking agent (2,5-dimethyl-2,5-di (t-butylperoxy) hexane, trade name “Perhexa 25B-40”, manufactured by NOF Corporation) and crosslinking assistant 1 part of an agent (divinylbenzene, trade name “divinylbenzene (purity 55%)”, Sankyo Chemical Co., Ltd.) was blended and mixed for 30 seconds using a Henschel mixer (Mitsui Mining Co., Ltd.). Thereafter, a twin screw extruder (model “PCM-45”, manufactured by Ikegai Co., Ltd., in the same direction fully meshing type screw), the ratio (L / D) between the length L of the screw flight part and the screw diameter D (L / D) is 33.5. And then extruding while subjecting to dynamic heat treatment under the conditions of staying at 230 ° C., 300 rpm, shear rate of 400 sec ⁻¹ for 1 minute and 30 seconds, to form a pellet-like dynamically crosslinked thermoplastic elastomer composition A product (Example 1) was obtained. The MFR of the obtained thermoplastic elastomer composition was 8 g / 10 min.

  The obtained thermoplastic elastomer composition was injection-molded using an injection molding machine (trade name “N-100” manufactured by Nippon Steel Works) to produce a sheet having a thickness of 2 mm, a length of 120 mm, and a width of 120 mm. . The produced sheet has a hardness (duro A) of 77, a tensile stress (100% modulus) of 3.6 MPa, a tensile stress (300% modulus) of 6.9 MPa, a tensile breaking strength of 6.9 MPa, and a tensile breaking elongation of 300%. The compression set was 28%, the tensile breaking strength change rate by the heat aging test was 3%, and the tensile breaking elongation change rate by the heat aging test was -7%.

(Examples 2-4, Comparative Examples 1-3)
Except that the formulation shown in Table 1 was used, a pellet-like dynamically cross-linked thermoplastic elastomer composition (Examples 2 to 4 and Comparative Examples 1 to 3) was prepared in the same manner as in Example 1 described above. ) The MFR of the obtained thermoplastic elastomer composition is shown in Table 1. In Table 1, “filler” is “calcium carbonate (trade name“ Whiteon 101 ”, manufactured by Shiraishi Calcium Co., Ltd.)”. The obtained thermoplastic elastomer composition was injection-molded by the same operation as in Example 1 to prepare a sheet. Table 1 shows the measurement results of various physical properties of the produced sheet.

  From the results shown in Table 1, the sheets produced using the thermoplastic elastomer compositions of Examples 1 to 4 are more elastic than the sheets produced using the thermoplastic elastomer compositions of Comparative Examples 1 to 3. It is clear that it is excellent in mechanical strength, flexibility, and heat resistance.

  The thermoplastic elastomer composition of the present invention is excellent in rubber elasticity, mechanical strength, flexibility, and heat resistance. For this reason, the thermoplastic elastomer composition of the present invention comprises automotive parts (bumpers, exterior moldings, wind seal gaskets, door seal gaskets, trunk seal gaskets, roof side rails, emblems, inner panels, door trims, door seals, Glass run channel), packing materials for electrical / electronic components (ink cartridges for inkjet printers, toner for copying machines, fuel cell stacks, flat panel displays (FPD) for liquid crystal displays, plasma displays, organic EL, SED devices, etc.) It can be widely used as a material.

Claims (7)

(A) a conjugated diene polymer rubber,
(B) an ethylene / α-olefin / non-conjugated diene copolymer rubber;
(C) a thermoplastic resin,
The content ratio of the (A) conjugated diene polymer rubber is 10 to 85 parts by mass,
The content ratio of the (B) ethylene / α-olefin / non-conjugated diene polymer rubber is 10 to 40 parts by mass, and
A raw material mixture in which the content ratio of the (C) thermoplastic resin is 5 to 50 parts by mass (however, (A) + (B) + (C) = 100 parts by mass)
(D) heat-treated dynamically in the presence of a crosslinking agent,
A thermoplastic elastomer composition having a durometer A hardness of 10 to 95 defined by JIS-K6253 and a compression set of 40% or less after heat treatment at 70 ° C. for 22 hours defined by JIS-K6262. The (A) conjugated diene polymer rubber is
The thermoplastic elastomer composition according to claim 1, wherein the monomer component containing the conjugated diene compound is polymerized using a rare earth element compound catalyst. The thermoplastic elastomer composition according to claim 2, wherein the rare earth element compound-based catalyst is a catalyst mainly comprising the following components (a) to (d).
(A) Component: Rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a compound obtained by reaction of these compounds with a Lewis base (b) Component: alumoxane (c) Component: AlR ¹ R ² R ³ (wherein, R ^{1 to} R ² are the same or different and are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents , Which may be the same as or different from R ¹ or R ² ) (d) Component: a halogenated silicon compound and / or a halogenated organosilicon compound Of the (A) conjugated diene polymer rubber,
1,4-cis bond content is 90% or more,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) as measured by gel permeation chromatography is 3.5 or less. A thermoplastic elastomer composition. The thermoplastic resin (C) is
The thermoplastic elastomer composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of a crystalline polyolefin resin and an amorphous polyolefin resin. For a total of 100 parts by mass of the (A) conjugated diene polymer rubber, the (B) ethylene / α-olefin / nonconjugated diene polymer rubber, and the (C) thermoplastic resin,
The thermoplastic elastomer composition according to any one of claims 1 to 5, comprising 200 parts by mass or less of a softener and / or a plasticizer.   A molded article comprising the thermoplastic elastomer composition according to any one of claims 1 to 6.